Diamine dioxide detergent compositions



United States Patent 3,234,139 DIAMINE DIOXIDE DETERGENT COMPOSITIONS Howard F. Drew, Wyoming, and Roger E. Zimmerer,

Springfield Township, Hamilton County, Ohio, assignors to The Procter 8: Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Original application Dec. 21, 1961, Scr. No. 161,307. Divided and this application Jan. 2, 1964, Ser. No. 335,373

Claims. (Cl. 252137) This is a division of Serial No. 161,307, filed December 21, 1961.

This invention relates to detergent compounds and com positions and more particularly to new and novel surface active diamine dioxides and compositions composed thereof.

In the constant improvement of organic detergent compounds, certain features have been found to be highly desirable. These features include resistance toward the ingredients imparting hardness to water, a high degree of detergency, and a capacity for solubilization of hard water soaps, such as calcium soap. Although there are a number of organic detergents which have these characteristics, detergent compounds having additional desirable characteristics find a wider scope of application.

An advantageous property for an organic detergent is a low degree of hygroscopicity which results in improved crystallinity. When detergent surface active agents which are hygroscopic are used in bar or granular forms desirable physical properties are impaired. Bars become soft and slimy and granules tend to cake and lose their free flowing and quick dissolving characteristics. For example, trialkylamine oxides have been found to be excellent detergent compounds but are so hygroscopic that they can be effectively used only in liquid detergent compositions.

On the other hand, a high degree of aqueous solubility is desirable since some well-known surface active agents such as akylbenzenesulfonate are very insoluble in water in the presence of other electrolytes and can only be used in liquid detergent compositions in conjunction with a suitable hydrotrope such as toluene sulfonate.

A high degree of detergency in cool or cold water is also highly desirable. Many fabrics such as those containing crease resistant additives should be washed in cool water to retain their crease resistant properties. Wool garments should be Washed in cool water. In some locations Warm or hot water is not available.

Detergent surface active agents which exhibit a high degree of mildness are particularly desirable.

It is a principal object of this invention to provide organic detergents and detergent compositions which have excellent detergency as well as a high degree of mildness and a low degree of hygroscopicity.

It is another important object to provide detergents and detergent compositions which have these characteristics and also have a high detergency in cool water.

It has been found that these and other objectives which will be apparent to those skilled in the art are achieved in the novel class of diamine dioxide compounds having the structure set forth below and in liquid and solid detergent compositions composed therefrom.

The diamine dioxides of this invention are:

In the above formula, R is an alkyl group having from to 18 carbon atoms; R R and R each are methyl, ethyl or propyl radicals and n is the Whole number 2 or 3. The arrows are the conventional representation for semipolar bonds.

Patented Feb. 8, 1966 "ice Examples of the compounds of this invention are:

N,N',N trimethyl N decyltrimethylenediamine-N,N-

dioxide,

N,N',N-triethyl-N-dodecylethylenediamine-N,N-dioxide,

N,N,N'- tripropyl N-tetradecylethylenediamine-N,N'-

dioxide,

N,N,N trimethyl N hexadecyltrimethylenediamine- N,N'-dioxide,

N,N,N' tripropyl N octadecyltrimethylenediamine-N,

N'-dioxide,

N methyl N',N' diethyl-N-octadecylethylenediamine- N,N-dioxide,

N,N' dimethyl N propyl N decylethylenediamine- N,N-dioxide and,

N,N diethyl N methyl N dodecyltrimethylenediamine-N,N'-dioxide.

Tertiary amine oxides as a broad class of compounds are known. However, diamine dioxides are new and novel. It is surprising to find in this new and novel class of compounds, compounds which have highly desirable properties as organic detergents.

It appears that only certain of the diamine dioxides have the aforementioned desired characteristics. If R is an alkyl group longer in chain length than 18 carbon atoms or shorter in chain length than 10 carbon atoms, desired detergency is not obtained. Likewise, if R R or R contain more than 3 carbon atoms, such characteristics are not obtained. Moreover, it has been found that the linkage between the amine groups must be no greater than three carbon atoms in order to realize the desired characteristics. A methylene linkage between the nitrogen atoms is difiicult to achieve inasmuch as the parent compounds are unstable. This instability undesirably affects the corresponding diamine dioxides.

When R R or R are alkyl radicals containing more than three carbon atoms, the compounds begin to lose their high solubility in the presence of an electrolyte. The nonhydroscopic properties of these compounds are also adversely affected. Surprisingly, those compounds containing one or more methyl groups have been found to exhibit especially outstanding sudsing properties.

In the diamine dioxides of this invention, the R alkyl group can be derived from naturally occurring fats and oils or from synthetic sources. Mixtures of diamine dioxides are very suitable wherein R varies in chain length from about C to C In the solid compositions, particularly granular products, an octadecylethylene or octadecyl trimethylene diamine dioxide or the tallow alkyl homologue thereof is preferred. The preferred compound for use in liquid compositions is the corresponding dodecyl or coco alkyl homologue thereof.

The diamine dioxides of this invention can be prepared by oxidizing corresponding diamines. A corresponding primary aliphatic diamine, in general, can be prepared by the method disclosed in US. Patent 2,754,330. Primary aliphatic diamines are prepared from glycols or amino alcohols by reacting the alcoholic compound with ammonia over a ruthenium catalyst.

Compounds of this invention are useful per se as detergents and surface active agents. Desirably, they are used with other materials to form built and unbuilt liquid and solid compositions, as for example, bar, flake, granular or tabletted granular compositions. It has been found in the liquid compositions built with a pyrophosphate compound, that N,N',N' trimethyl-N-dodecylethylenediamine-N,N'-dioxide gives the most unusual and desirable results. On the other hand, N,N, trimethyl-N-octadecyletliylenediamine-N,N'-dioxide gives unusual and outstanding results in a granular or other solid product.

The solid form detergent compositions of this invention can contain from about 5% to of the instant diamine dioxides and from 95% to about 20% of normally solid anionic organic detergents, nonionic organic detergents, water soluble inorganic alkaline buildersalts, water soluble organic alkaline sequestrant builders salts and mixtures thereof. The liquid compositions of this invention contain in addition to these other actives and additives from about 2% to about. 30% of the diamine' dioxides of this invention in a liquid vehicle.

Granular or flake detergents preferably contain about 5% to about 50% of the diamine dioxides of this invention and from about 95% to about 50% normally solid, water soluble inorganic alkaline builder salts, or organic.

to about 80% of the diamine dioxides of this invention as the. only detergent component, if desired,and the balance inert fillers or builders.

Anionic organic detergents. used alone or in admixture include both the soap and non-soap detergents. Examples of suitable soaps are the sodium,-potassium, ammonium. and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic nonsoap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or-sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-methyl taurides; alkylbenzenesul-i fonates; alkyl phenol polyethenoxy sulfonates. In'these compounds the alkyl andacyl groups, respectively, contain to carbon atoms. They are used in the form oxide and ethylene diamine wherein the molecular weight.

of the condensation products range from 5000 to 11,000; the condensation product of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched. chain aliphatic alcohol containing from 8 to 18 carbon;

atoms (e.g., lauryl alcohol)- Water-soluble inorganic alkaline builder salts used alone or in admixture are alkali metalcarbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.

Ammonium or substituted ammonium salts can also be used. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate,

sodium pyrophosphate, sodium bicarbonate, potassium,

tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-ortho phosphate and potassium bicarbonate- .Such a inorganic builder salts enhance the detergency of the subject diamine dioxides.

Examples of Water-soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal,

alkali metal salts of phytic acid, e.g., sodium phytate Mixed salts of these polycarboxylates are also suitable. .The.

are also suitable .as organic sequesteringv agents: (see US Patent 2,73 9,942).

The preferred solid form detergent compositions con-..

tain about. 10% to about 30% ofthe diamine dioxides of the invention andat least an equal amount of sodium tripolyphosphate. Desirably the higher alkyl dia'mine di oxides wherein the .alkyl radical ranges from 16 to 18 carbon atoms in.chain length are used insuch preferred compositions.

The preferred built liquid detergent compositions contain about 5% to about 30% .of the diamine dioxides-of the invention and about 5% to 40% ofpotassiumpyrophosphate in a liquid vehicle. Desirably thelower alkyl diamine dioxides wherein the. alkyl. radicalranges from .10 to 12 or 14 carbon atoms inilength'are used in such preferred compositions.

The detergent compositions. of this invention canconv tain any of the ,usual adjuvants, diluents: and additives,- for example, ampholytic or .zwitterionic detergents, cationic detergents, perfumes, anti-tarnishing; agents, anti-' redeposition agents, bacteriostatic agents, dyes, fluorescers, oxygen or chlorine .bleaches, suds bui1ders, suds depressors, and the like. Thefollowing examples illustrate the preparation of diaminedioxides compounds" and ,compositionsof this invention.

EXAMPLE I I Eighty-eight grams (1.0 mole) of N,N-dimethylethylenediamine, obtained from Chemical Research andIntermediates'Laboratories, were dissolved, in 1000 mls. of

anhydrous diethyl ether contained in a 2-liter, 3-necked,.

round-bottom, glass flask equipped .witha reflux :condenser protected with a drying tube, mechanicalstirring assembly, and a pressure compensated additionfunnel.

layer was separated The ether was evaporated, the.

residue taken up 'in-acetone. and dried with anhydrous sodium carbonate. The drying agent-was removed by filtration and the acetone evaporated on a steambath to. yield. 114 grams (42% of theory) N,N-dimethyl-N'-' lauroylethylenediamine.

Calculated for CHI-134N201 percent N, 10.4. Found percent .N, 10.1.

Thirty-eight grams (1.0 mole) of powdered lithium aluminum hydride were combined with 600 mls. of an-.

hydrous diethyl ether in a 1-liter, glass, round-bottom flask surmounted with a Soxhlet extraction apparatus containing 113 grams (0.41 mole) N,N-dimethyl-N'-lauroylethylenediamine in a paper extraction thimble. The apparatus was heated electrically to 35 C. Reaction pro-- ceeded by the gradual solution of the amide in the ether and'periodic siphoning. of this solution into the reactor. Reflux was maintained at 35 C. for 6 hours, atwhich time the excess lithium {aluminum hydride was decomposed with ethyl acetate. The mixture wasacidified with:

dilute HCl to break up salts and complexes. After basification with dilute sodium hydroxide the resulting suspension was extracted with'petroleum ether. The organic (ether) layer was separated, dried over anhydrous sodium sulfate, filtered, and the petroleum ether removed on a steam bath to yield 105 grams (100% of theory) of crude N,N-dimethyl-N dodecylethylenediamine.

One hundred and five grams (0.41 imole) of crude N,N'-dimethyl-N dodecylethylenediamine were combined with-102 grams. (2 moles) of formic acid. in a 500 Sixty-three ml.- 1- necked,: glass, round-bottom flask. grams formalin (0.75 mole of formaldehyde) were added to this solution. 7

A reflux condenser: was installed; A vigorous reactionensued-accompanied by considerable foaming. This was controlled by periodic cooling to about 90 C. in a cold water bath. Reflux temperature (100 C.) was maintained until the evolution of CO had almost ceased (3 /2 days). The mixture was combined with 150 mls. of concentrated HCl and heated to 100 C. on the steam bath to remove excess formaldehyde and formic acid. The solution was made basic with 30% aqueous sodium hydroxide solution, the layer of amine separated and distilled through a 1 foot Vigreux column at a pressure of 1 mm. of mercury. The fraction boiling from 130135 C. with 11 1.4475 was collected. This fraction weighed 71 grams representing a yield 64% of theory for N,N,N'-trimethyl-N-dodecylethylenediamine.

Calculated for C H N percent N, 10.4. Found: percent N, 10.0.

Forty grams (0.15 mole) of N,N',N-trimethyl-N-dodecylethylenediamine were dissolved in a mixture of 150 mls. of formula 3A alcohol (ethanol denatured with methanol) and 50 mls. of water contained in a 500 ml. glass, round-bottom flask equipped with a mechanical stirring assembly, reflux condenser, and thermometer. To this solution were added 51 grams of 30% aqueous H (0.45 mole). The mixture was stirred and the temperature maintained at 50-60 C. for hours. After standing overnight at room temperature the mixture was diluted with 300 mls. of water and the excess peroxide decomposed catalytically with platinum black. The spent catalyst was removed by filtration and the unreacted amine (1.3 grams) was removed by a triple extraction with petroleum ether. The alcohol was removed on the steam bath under a current of nitrogen. The residual solution was freeze-dried to yield 45 grams of hydrated N,N',N' trimethyl N dodecylethylenediamine N,N- dioxide representing a 94% yield.

Calculated for C H N O -2H O: percent C, 60.4; percent H, 12.5; percent N, 8.28; percent reducible O, 9.47; percent H O. 10.6. Found: percent C, 61.6; percent H, 12.5; percent N, 8.37; percent 0 (SnCl reduction), 9.38; percent H O (vacuum oven) 10.0.

By substituting N,N-diethylethylenediamine for N,N- dimethylethylenediamine as the starting material in this example, N,N'-diethyl-N-methyl-N-dodecylethylenediamine-N,N'-dioxide was obtained.

EXAMPLE II In a 5-liter, B-necked, glass, round-bottom flask equipped with a reflux condenser, addition funnel, and mechanical stirring assembly were placed 300 grams (5 moles) ethylenediamine, obtained from Matheson, Coleman and Bell, dissolved in 150 mls. of formula 3A alcohol. This solution was stirred while 333 grams (1 mole) of octadecyl bromide dissolved in 2 liters of formula 3A alcohol were added over a period of 1 /2 hours. The temperature was raised to a reflux (77 C.) by means of an electric heating mantle. Stirring and heating were continued for about 6 hours. At this point 1000 mls. of alcohol were removed by distillation and 1 liter of 1 N sodium hydroxide added to the cooled concentrate. The resulting water/alcohol system was extracted with warm heptane. Upon evaporation of the heptane 300 grams of crude octadecylethylenediamine were obtained. This represents a yield of 96%.

Calculated for C H N Neutral equivalents, 313 and 156 for the first and second nitrogen, respectively. Found: Neutral equivalents, 307 and 169.

Into a 2 liter, 3-neclred, glass, round-bottom flask, equipped with reflux condenser and mechanical stirring assembly were placed 115 grams (0.37 mole) of octadecylethylenediamine, 225 grams (4.4 moles) 90% formic acid, and 122.5 grams formalin (1.47 mole formaldehyde). Occasional cooling to about 90 C. with a cold water bath was required in the early stage of the reaction to reduce foaming. Stirring at reflux temperature (100 C.) was maintained for 3 days. The resulting solution was transferred to an evaporating dish, 150 mls. of concentrated HCl added and the excess formaldehyde and formic acid removed on a steam bath by heating to C. The resulting solution was poured into a mixture of 1000 grams of crushed ice and 400 mls. of 30% aqueous sodium hydroxide solution. The solids were removed by filtration, taken up in ether, washed with water, and the ether removed by evaporation on a steam bath. The resulting dark brown product consisted of 51 grams of liquid and 62 grams of paste-like solid. Infrared spectra indicated the liquid was completely methylated (no N-H bands were detected) while the solid was incompletely methylated. The liquid portion was distilled at 0.1 mm. mercury pressure through a 1 ft. Vigreux column to yield 30 grams boiling from 156- 161 C. with n 1.4532.

The 30 grams (0.08 mole) of the ditertiaryamine prepared above were combined with 240 mls. of formula 3A alcohol, 80 mls. of water, and 28 grams of 30% aqueous H 0 solution (0.25 mole) in a 500 ml. glass, roundbottom flask equipped with a mechanical stirring assembly, thermometer, and reflux condenser. The reaction was stirred for about 8 hours at 50-60 C. After cooling to room temperature, mls. of water were added and the excess H 0 decomposed catalytically using platinum black. After removal of the spent catalyst by filtration, the solution was extracted with petroleum ether to re move unreacted arnine (1.5 grams). The alcohol was removed by evaporation on a steam bath under a stream of nitrogen and the product isolated from the remaining solution by freeze-drying. A yield of 29.5 grams (about 87% of theory) of hydrated N,N',N-trimethyl-N-octadecylethylenediamine-N,N'-dioxide was obtained.

Calculated for C H N O -H O: percent C, 68.2; percent H, 12.9; percent N, 6.92. Found: percent C, 67.8; percent H, 12.6; percent N, 6.94.

EXAMPLE III N,N- diethylethylenediamine, obtained from Eastman Kodak Co., was converted to N',N-diethyl-N-dodecylethylenediamine following the procedure given in Example I. This amine was convert-ed to N,N,N-triethyl- N-dodecylethylenediamine in a manner analogous to the methylation in Example I except that acetaldehyde was used in place of formaldehyde. The oxidation was carried out in the same manner as above to give N,N',N'- triethyl-N-dodecylethylenediamine-N,N'-dioxide.

EXAMPLE IV N,N,N' tripropyl-N-tetradecylethylenediamine-N,N- dioxide was prepared in a manner analogous to that given in Example If except that tetradecyl bromide and propionaldehyde were substituted for octadecyl bromide and formaldehyde respectively.

EXAMPLE V es Following the procedure outlined in Example II but substituting 1,3-diaminopropane and dodecyl bromide for ethylenediamine and octadecyl bromide respectively, N,N,N trimethyl N dodecyltrimethylenediamine- N,N'-dioxide was obtained.

EXAMPLE VI N,N,N trimethyl N dodecylethylenediamine-N,N'- dioxide, prepared in the manner described in Example I, was determined to be substantially superior to sodium dodecylbenzenesulfonate wherein the dodecyl group was derived from tetrapropylene in the cloth-swatch deterency test described below. Sodium dodecylbenzenesulfonate is a widely used detergent active for laundering compositions and is, therefore, a reasonable standard for comparison.

This test involved washing naturally soiled cloth (desized print cloth) in a 0.1% aqueous solution of a comosition com risin 20% or anic deter ent com ound (diamine dioxide being tested or the alkylbenzenesulfonate standard), 50% sodium tripolyphosphate and 30% sodium sulfate. and the washing was done at 140 F. for minutes using wash water of 7 grains per gallon hardness. The detergency effectiveness was determined by measuring the percentage of lipid soil remaining on a standard size swatch (on a dry basis) after the washing operation. The percentage of lipid soil remaining after washing with the diamine dioxide test composition was compared with the percentage after washing with the alkylbenzene sulfonate standard composition. On the basis of the percent residual lipid soil, the. lower the percent, the better the detergency performance. The test indicated that the percent residual lipid soil remaining on the test swatch after washing with the N,N",N' trimethyl N'- dodecy ethylenediamine-N,N'-dioxide composition was substan tially less than that remaining after washing with the sodium dodecylbenzenesulfonate standard composition.

The composition had a pH of 10.0

The hygroscopicity of N,N,N'-trimethyl N dodecyl- I ethylenediamine-N,N-dioxide was determined by exposing dry recrystallized material in a constant 50% relative humidity chamber at 70 B; it had weight increases of about 4.0% after 2 days and about 15% after 7 days in this hygroscopicity test. ide, a known detergent active, had weight increases of 32% after 1 day and 30% after 7 days. It is apparent that the former compound is much less hygroscopic than the latter;

N,N,N-trimethyl-N dodecylethylenediamine N,N'- dioxide has'been found to exhibit an unexpectedly high degree of mildness. It is also an effective mildness additive for other detergents. On a comparative basisin a standard, but exaggerated, mildness test, using guinea pigs with shaved undersides, partially immersed in aqueous.

- Dim-ethyldodecylamine .ox-

equivalent hygroscopicity characteristics, mildness char acteristics, and detergent efiicacy. The solubility in elec- EXAMPLE lVII In addition to the performance tests of Example VI, N,'N,N'-trimethyl N-octadecylethylenediamine N,N- dioxide was evaluatedin an extensive wash-wear test by washing naturally soiledwhite dress shirts worn by male subjects under ordinary conditions for two normal days. The degree to which adetergent compositioncontaining a detergent compound to. be tested cleaned the collarsand cuffs of the soiled shirts, relative to the cleaning degree of a similar composition containing a standard detergent compound,lwas considered a measure of the detergency effectiveness of the test compound.

The washing solutions used in the. wash-Wear test contain 0.03% organic detergent compound and 0.06% sodi um tripolyphosphate. (No fluorescers, bleaches, or antiredeposition agents are used.) The, pH of the washing solution is 10 and water. of 7 grains per gallon hardness is used. A conventional, agitator-type washer and wash water of 130 F. are vused. The detergent compound in the standard detergent composition is sodium dodecylbenzenesulfonate, the most commonly used organic detergent surfaceactive agent in heavy duty laundry detergent'compositions. Thetest detergent composition con test solutions, N,N,N-trimethyl N-dodecylethylenedi- 1 amine-N,N-dioxide was scored as an 8 on a scale of 1 to 10 wherein the highest score indicates the highest degree of desirable mildness and 1 is severe irritation. Sodium dodecylbenzenesulfonate was scored as 4. At least three or more test solutions of 0.2% detergent active were averaged in tabulating the results. solution consisting of 0.2% of sodium dodecylbenzenesulfonate plus 0.1% of N,N,N-trimethyl-N-dode-cylethylenediamine-N,N-dioxide was scored as 9, showing the additive mildness effect of the diamine dioxides and the,

sulfonate.

The solubility of N,N',N-trimethyl-N-dodecylethylenediamine-N,N-dioxide in aqueous electrolyte solutions was determined by adding known amounts of diamine dioxide to known amounts of tetrapotassium pyrophosphate and tetrapotassium ethylenediamine tetraacetate (Ki EDTA). No hydrotroping agents were used. It was foundthat 100 grains of 20% aqueous K EDTA at roorntemperature. In the case of K pyrophosphate, the results showed that more than 16 grams of diamine dioxide were soluble in 100 grams of 20% aqueous electrolyte. The generally high solubility of the diamine dioxide in aqueous solutions of electrolyte is apparent from the solubility of.

N,N-dioxide has performance characteristics.snbstantially similar in all respects tothose of. N,N,N--trimethyl- N dodecylethylenediamine- N,Ndioxide. The other. diamine dioxides of this invention will have substantially An aqueous test L more than 21 grams of diamine dioxide were soluble in tains the detergent compound to the compared with the detergent compound in the standard compositions.

In the instant test, N,N',N'-trimethyl-N-octadecylethylenediamine-N,N-dioxide was preferred over the standard test composition in general, detergency eifectiveness.

The surprising cool water detergency powers of .the diamine dioxides of this invention was demonstrated by the results obtained in the swatch test of Example Vl wherein the test swatches were washed in aqueoussolution containing sodium dodecylbenzenesulfonate at 140 F." for 10 minutes 'and aqueous solution containing- N,N',N trimethyl-N-octadecylethylenediamine N,N'- dioxide ,at F: for 10 minutes. The percentage of lipid soil remaining on the swatches after washing with the diamine dioxide solution at low temperature is found to be about equivalent to. that remaining after washing with the sodium dodecylbenzenesulfonate standard composition at- 140 'F. and is substantially superior tozthat of the standard com-position at 80 F. A further comparison of N,N,N'-trimethyl-N-octadecylethylenediarnine- N,N-dioxide with dimethyldodecylamine oxide shows that both-of these amine oxide compounds have substantially equivalent cool to 'tepidwater (40 F. to F.) washing characteristics.

The diaminedioxides-of-this invention can be usedin effective solid 'form detergent compositions having. improved hygroscopicity, desirable mildness and ,detergency efiicacy. The :following formulations have these characteristics:

Granular. detergent Percent N,N'-,N'-trimethyl-N-octadecylethylenediamine- N,Ndioxide 17.5

Sodium sulfate I 9 Granular detergent Percent N,N',N'-tripropyl-N-tetradecylethylenediamine= N,N-dioxide 1O Condensation product of one mole of nonyl 5 .phenol and nine moles of ethylene oxide Sodium pyrophosphate 50 Sodium carbonate 3 Trisodium phosphate 3 Sodium sulfate 24 10 Milled toilet bar Percent N,N,N' trimethyl N alkyltrimethylenediamine- N,N'-dioxide (the alkyl group being derived from coconut fatty alcohol) 10 Sodium coconut oil soap 15 Sodium tallow soap 65 Moisture 10 Milled toilet bar Percent N,N,N triethyl N tetradecyltrimethylene diamine-N,N'-dioxide 50 Tallow fatty acid 25 Moisture 15 Cornstarch 5 Triethanol ammonium ethylenediamine-tetraacetate 5 Securing cleanser Percent Silica flour 85 Detergent consisting of 85% trisodium phosphate and 15% N,N',N trimethyl N octadecylethylenediamine-N,N'-dioxide 15 The diamine dioxides of this invention find particularly desirable utilization in liquid form detergent compositions. Liquid form detergent compositions provide convenience in use, particularly for measurement and dispensing operations. Liquid detergent compositions can 40 be in the form of solution, dispersions or emulsions. Preferably, they can contain from about 5% to about 30% of the diamine dioxides of this invention and from about 5% to about 40% of a water-soluble inorganic alkaline builder salt or an organic alkaline sequestrant builder salt, the balance of the composition being a solvent, such as water, and/or other liquid vehicles.

Examples of liquid detergent compositions including the diamine dioxides of'this invention are as follows:

Liquid detergent Percent Sodium dodecylbenzenesulfonate 6 N,N,N trimethyl N dodecylethylenediamine- N,N'-dioxide (the alkyl being derived from distilled coconut oil fatty alcohol) 6 Potassium pyrophosphate 20 Potassium toluene sulfonate 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0 3 6 Water Pvt-..fluu-wuw ru Ba a e 10 Liquid detergent Percent N,N' dipropyl N methyl N decyltrimethylenediamine-N,N'-dioxide 10 Tetrasodium ethylenediaminetetraacetate 25 Water As many apparently different embodiments of this invention may be made Without departing from the spirit and scope thereof, it is understood that this invention is not limited to the specific embodiments or specific examples thereof except as defined in the appended claims.

What is claimed is:

1. A detergent composition consisting essentially of from about 5% to about of N,N',N-trimethyl-N- alkylethylenediamine-N,N-dioxide wherein said alkyl ranges in chain length from 10 to 18 carbon atoms and about to about 20% of a builder selected from the group consisting of water-soluble inorganic alkaline builder salts, Water-soluble organic alkaline sequestrant builder salts, and mixtures thereof.

2. A detergent composition in solid form consisting essentially of from about 5% to about 50% of N,N,N- trimethyl-N-alkylethylenediarnine-N,N-dioxide wherein said alkyl ranges in chain length from 10 to 18 carbon atoms and about 95% to about 50% of a normally solid builder selected from the group consisting of water-soluble inorganic alkaline builder salts, Water-soluble organic alkaline sequestrant builder salts, and mixtures thereof.

3. A detergent composition in solid granular form consisting essentially of from about 5% to about 50% of N,N',N trimethyl N alkyletl-lylenediamine N,N- dioxide wherein said alkyl ranges in chain length from 10 to 18 carbon atoms and about 95% to about 50% sodium tripolyphosphate.

4. A detergent composition in solid granular form consisting essentially of from about 5% to about 50% of N,N',N trimethyl N octadecylethylenediamine- N,N-dioxide and about 95 to about 50% sodium tripolyphosphate.

5. A liquid detergent composition consisting essentially of from about 5% to about 30% of N,N,N-triinethyl- N-dodecylethylenediamine-N,N'-dioxide; and about 5% to about 40% potassium pyrophosphate; balance Water.

References Cited by the Examiner UNITED STATES PATENTS 2,169,976 8/1937 Guenther et al. 252-152 2,999,068 9/1961 Pilcher et al. 252137 3,001,945 9/1961 Drew et a1. 252-137 XR 3,047,579 7/1962 Witman 260-583 XR 3,085,982 4/1963 Steer et a1. 252137 3,086,943 4/1963 Lang 252l52 OTHER REFERENCES Jerchel et al.: Chemical Abstracts, v01. 48 (1954), p. 1246.

JULIUS GREENWALD, Primary Examiner.

ALBERT MEYERS, Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 5% TO ABOUT 80% OF N,N'',N''-TRIMETHYL-NALKYLETHYLENEDIAMINE-N,N''-DIOXIDE WHEREIN SAID ALKYL RANGES IN CHAIN LENGTH FROM 10 TO 18 CARBON ATOMS AND ABOUT 95% TO ABOUT 20% OF A BUILDER SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE INORGANIC ALKALINE BUILDER SALTS, WATER-SOLUBLE ORGANIC ALKALINE SEQUESTRANT BUILDERS SALTS, AND MIXTURES THEREOF. 